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Catalysis in organometallic CVD of thin metal films

  • US 5,403,620 A
  • Filed: 10/13/1992
  • Issued: 04/04/1995
  • Est. Priority Date: 10/13/1992
  • Status: Expired due to Term
First Claim
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1. A process for the chemical vapor deposition of at least one metal onto a substrate comprising:

  • a) exposing said substrate to a fluid mixture containing a major amount of at least one vaporizable or soluble precursor film forming metal compound having the formula
    
    
    space="preserve" listing-type="equation">L.sub.n MR.sub.mand to a fluid containing a minor amount of at least one vaporizable or soluble precursor catalytic metal compound having the formula
    
    
    space="preserve" listing-type="equation">L.sub.n M'"'"'R.sub.mwherein L is a π

    -bonding organic ligand consisting of ethylene, allyl, methylallyl, butadienyl, pentadienyl, cyclopentadienyl, methycyclopentadienyl, cyclohexadienyl, hexadienyl, cycloheptatrienyl, or alkyl or alkyl silyl or fluorinated derivatives of said precursor catalytic metal compounds having sufficient volatility of the precursor metal compound to be of utility in gaseous CVD or liquid CVD;

    M is a precursor metal consisting of a transition metal, Ti (titanium), Zr (zirconium), Hf (hafnium), V (vanadium), Nb (niobium), Ta (tantalum), Cr (chromium), Mo (molybdenum), W (tungsten), Mn (manganese), Re (Rhenium), Fe (iron), Ru (ruthenium), Os (osmium), or a main group metal consisting of Al (aluminum), Ga (gallium), In (indium), a group 4a element consisting of Si (silicon), Ge (germanium), Sn (tin), or a lanthanide or actinide metal consisting of La (lanthanum), Nd (neodymium), Sm (samarium), U (uranium), Pu (plutonium;

    M'"'"' is a metal selected from the group of metals that can catalyze hydrogenation and hydrogenolysis reactions of unsaturated and saturated organic ligands, L and R, to yield volatile byproducts and also can catalyze the hydrogenation of surface carbon to methane in the presence of hydrogen, and consisting of the Group VIII transition metals of Co (cobalt), Rh (rhodium), Ir (iridium), Ni (nickel), Pd (palladium), Pt (platinum), Fe (iron), Ru (ruthenium), and Os (osmium);

    R is a σ

    -bonding ligand radical consisting of hydrogen, methyl, ethyl, n- or iso- propyl, n-, sec-, or t- butyl, benzyl, phenyl, and silylated and fluorinated derivatives having sufficient volatility or solubility of the precursor metal compound to be of utility in CVD or liquid CVD;

    n is a number from 0 to the valence of said metal,m is a number from 0 to the valence of the metal, where m plus n allow a stable configuration of the precursor metal compound to allow the precursor compound to be either volatile or soluble in an organic solvent;

    (b) exposing said substrate to hydrogen gas; and

    (c) maintaining said substrate throughout the reaction at a temperature sufficiently high to decompose said precursor film forming metal compounds and said precursor catalytic metal compounds;

    (d) reacting said precursor film forming metal compound and said precursor catalytic metal compound in the presence of hydrogen gas in a manner to cause decomposition of precursor metal compound Ln MRm, and of the catalyst metal compound Ln M'"'"'Rm on the surface of said substrate to form on said surface a metal film M containing catalytic metal M'"'"' without causing substantial impurities from the ligands of said precursor compounds to be formed on said surface and incorporated on or within said metal film.

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